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研究生: 施宏道
Heng-Dau Shr
論文名稱: 多面體寡體矽石/甲基丙烯酸脂系之奈米結構
Study polyhedral oligomeric silsequioxanes/ methylacrylate nanostructured hybrid materials
指導教授: 徐新興
Shin-Shing Shyu
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
畢業學年度: 91
語文別: 中文
論文頁數: 70
中文關鍵詞: 甲基丙烯酸脂多面體寡體矽石奈米結構
外文關鍵詞: nanostructured, Study polyhedral oligomeric silsequioxanes, methylacrylate
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  • 本實驗以Methyl methacrylate (MMA)單體為主,加入與MMA相似官能基Acrylates系統的多面體矽氧烷寡聚物 (Polyheral Oligomeric Silsesquioxanes,POSS)。POSS又細分為兩種,一為MethacrylIsobutyl -POSS【POSS(MA0702)】,另一個為MethacrylEthyl-POSS【POSS(MA0717)】,兩者雙鍵官能基的部分是一樣的,唯一不同的是在Si-O外的碳氫化合物支鏈,分別為butyl與methyl,其分子量分別為943.64g/mole 和747.27g/mole。藉由奈米粒子POSS與MMA共聚合,來改善PMMA性質。
    由FTIR、NMR、DSC、GPC的結果,當POSS重量比例低於20wt%,Free radical:AIBN重量比為1wt%,MMA與POSS能產生共聚合效果,當POSS重量比例超過20wt%時,共聚合效果並不好。加大AIBN重量比為2.5wt%時,POSS重量比例超過20wt%,才能與MMA產生共聚合效果。就不同POSS比較,發現POSS(MA0717)與MMA共聚合效果比POSS(MA0702)好。
    由TGA結果可發現,當POSS重量比例越高時,其材料的裂解溫度會越高,同時到了700℃後,殘留量也會隨著POSS的量而增加。材料機械性部分,利用照相以及DMA的分析可知,隨著POSS重量比例的增加,材料硬度也跟著增加;但是POSS重量比例超過20 wt%,材料因為過於硬脆而無法成型,隨著POSS比例越高時,材料成形結果越差。另外由TMA結果發現,材料的Tg點也會隨著POSS重量比例的增加而增加。
    最後利用照相以及DMA的分析發現,PMMA本身即為透明材料,當POSS共聚合後,材料仍然成透明狀,所有比例共聚合,於可見光範圍下,透光率居只有0.15~0.35之間,非常透明的狀態。


    A series of novel hybrid Methyl methacrylate (MMA) and Polyheral Oligomeric Silsesquioxanes(POSS) are synthesizedand characterized. MethacrylIsobutyl -POSS【POSS(MA0702)】and MethacrylEthyl-POSS【POSS(MA0717)】 have been investigated. Both compounds have the same Acrylates groups, but the inorganic Si8O12 spherical core of POSS surrounded by seven inert organic corner groups are different. One is butyl, the other is methyl. Molecular weights are 943.64g/mole and 747.27g/mole respectively. The influence of the weight fraction of POSS and the corner group composition on properties have been examined.
    The prepared polymer hybrids were characterized by FTIR、NMR、DSC、GPC.When the random copolymer contain 20wt% POSS monomer and 1wt% AIBN, the polymer copolymerized completely. While the random copolymer contain more than 20wt% POSS monomer, AIBN must be added 2.5wt%, the polymer copolymerized completely. The copolymerizatoin of MMA with POSS(MA0702) and POSS(0717) respectively, POSS(MA0717)is well reactor than that of POSS(MA0702).
    TGA, DMA, TMA and picture of digital camera show that the Td, Tg and roughness is increased as the increased of the ratio of POSS. When the temperature over 700℃, the residual weight increase with increasing the ratio of POSS.
    As the result of digital camera and UV, when POSS copolymerized with MMA, the material is also transparent. Under the range of visible , the transmittance is about 0.15~0.35.

    目錄 目錄…………………………………………………...……………... I 圖目錄………………………………………………..……………… IV 表目錄………………………………………………………………. IV 中文摘要………………………………………………….…………. VIII 英文摘要(Abstract)…………………………………………….. IX 第一章 序論………………………………………………………… 1 第二章 文獻回顧…………………………………………………… 4 2-1 奈米技術………………………………………………………. 4 2-2 多面體矽氧烷寡聚物 (Polyheral Oligomeric Silsesquioxane,POSS) …………………………………………… 5 2-2-1多面體矽氧烷寡聚物(POSS)的定義與結構…….………….. 5 2-2-2多面體矽氧烷寡聚物(POSS)的製備…………….………….. 8 2-2-3多面體矽氧烷寡聚物(POSS)與高分子單體共聚合………... 11 2-2-4多面體矽氧烷寡聚物(POSS)的特性………………………... 17 第三章 實驗部分…………………………………………………… 22 3-1實驗目的………………………………………………………... 22 3-2 實驗藥品……………………………………...………………... 22 3-3實驗儀器………………………………………………………... 24 3-3-1 實驗儀器一覽表…………………………………………….. 24 3-3-2 傅立葉紅外線光譜分析儀FTIR(Fourier Transform Infrared Spectrometer) …………………………………………. 25 3-3-3 固態核磁共振儀 NMR (Solid Nuclear Magnetic Resonance) …………………………………………………………. 25 3-3-4 熱式差掃描卡量計DSC (Differential Scanning Calorimetry) ………………………………………………………. 25 3-3-5 膠質滲透層析儀 GPC (Gel Permeation Chromatography) …………………………………………………… 25 3-3-6 熱重量分析儀 TGA (Thermal Gravimetric Analyzer) …………………………………………………………… 26 3-3-7 數位相機(Digital Camera)……………………………….. 26 3-3-8 熱機械分析儀 TMA (Thermomechnical Analysis) …………………………………………………………… 26 3-3-9 動態機械分析儀 DMA (Dynamics Mechnical Analyzer) …………………………………………………………… 26 3-3-10 紫外/可見光光譜分析儀 UV (UV-Visible) …………….. 27 3-4 實驗步驟………………………………………………………... 27 第四章 結果與討論…………………………………………………. 30 4-1 傅立葉紅外線光譜分析FTIR(Fourier Transform Infrared Spectrometer) ……………………………………………………… 30 4.2 固態核磁共振NMR (Solid Nuclear Magnetic Resonance) ………………………………………………………….. 30 4.3 熱視差掃描卡量計DSC (Differential Scanning Calorimetry) ……………………………………………………….. 35 4.4 膠質穿透層析儀 GPC (Gel Permeation Chromatography) …………………………………………………… 37 4.5 熱重量分析儀 TGA (Thermal Gravimetric Analyzer) …………………………………………………………… 43 4.6 數位相機(Digital Camera) ………………………………….. 54 4.7 熱機械分析TMA (Thermomechnical Analysis) ……………. 54 4.8 動態機械分析DMA (Dynamics Mechnical Analyzer) ……… 58 4.9紫外/可見光光譜分析UV (UV-Visible) …………………….. 60 第五章 結論…………………………………………………………. 64 參考文獻……………………………………………………………... 66 圖目錄 圖1-1、高分子奈米複合材料演進歷程(一) ……………………… 2 圖1-2、高分子奈米複合材料演進歷程(二) ……………………… 3 圖2-1 梯形(Labber)與多面體(Polyhedron)結構之矽氧烷 ………. 5 圖2-2 多面體矽氧烷結構 ………………………………………… 6 圖2-3 T8多面體矽氧烷結構之鍵角與鍵長 …………………….. 7 圖2-4 多面體矽氧烷結構誤認為cube狀 ……………………….. 8 …圖2-5多面體矽氧烷結構為cage狀 …………………………… 8 圖2-6 合成多面體矽氧烷寡聚物(POSS)步驟圖 ………………… 10 圖2-7 合成多面體矽氧烷寡聚物(POSS)步驟圖 ………………… 10 圖2-8多面體矽氧烷寡聚物(POSS)結構分類圖 …………………. 11 圖2-9多面體矽氧烷寡聚物(POSS)共聚合狀態 …………………. 13 圖2-10 Methystyrene與Styryl-Based-POSS的聚合方程式 …….. 14 圖2-11 Norbornene與POSS-Norbornyl的聚合方程式 …………. 15 圖2-12多面體矽氧烷寡聚物(POSS)可接枝之官能基 …………... 15 圖2-13多面體矽氧烷寡聚物(POSS)可接枝之官能基 ………….. 16 圖2-14多面體矽氧烷寡聚物(POSS)功能圖 …………………….. 17 圖2-15 多面體矽氧烷寡聚物(poss)奈米材料分布情形 ………… 18 圖3-1 MMA與POSS的共聚合實驗 …………………………….. 28 圖3-2 高分子粉末熱壓實驗 ……………………………………… 29 圖4-1多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為1wt% FTIR吸收光譜儀 ………………………. 31 圖4-2多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為2.5wt% FTIR吸收光譜儀 ……………………… 32 圖4-3多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,AIBN為1wt% FTIR吸收光譜儀 ……………..…………. 33 圖4-4多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,AIBN為2.5wt% FTIR吸收光譜儀 …………..………….. 34 圖4-5多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,C13-NMR………………………………………………………….. 36 圖4-6多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為1wt% DSC分析圖 .…………………………… 38 圖4-7多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為2.5wt% DSC分析圖 …………………………… 39 圖4-8多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,AIBN為1wt% DSC分析圖 ……………………………… 40 圖4-9多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,AIBN為2.5wt% DSC分析 ……………………………… 41 圖4-10多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為1wt% GPC分析圖 …………………………… 44 圖4-11 多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為2.5wt% GPC分析圖 ………………………… 45 圖4-12多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,AIBN為2.5wt% GPC分析圖 ………………………… 46 圖4-13多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,AIBN為2.5wt% GPC分析 …………………………… 47 圖4-14多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合, 分子量一覽表 ……………………………………………………… 48 圖4-15多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合, 高分子聚合度一覽圖 49 圖4-16多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,TGA分析圖 …………………………………………… 52 圖4-17多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,TGA分析圖 ……………………………………………. 53 圖4-18多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,照相分析圖 …………………………………………… 55 圖4-19多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,照相分析圖 ……………………………………………………..….. 56 圖4-20多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,照相分析圖 ………………………………………………………… 57 圖4-21多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,DMA分析圖……………………………………………………..….. 59 圖4-22多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,DMA分析圖……………………………………………………..….. 61 圖4-23多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,UV分析圖………………………………………………. 62 圖4-24多面體矽氧烷寡聚物POSS(MA0717)與MMA以不同比例共聚合,UV分析圖………………………………………………. 63 表目錄 表2-1多面體矽氧烷寡聚物(POSS)與高分子共聚方式優缺點…... 16 表2-2多面體矽氧烷寡聚物(POSS)與其他填充料之特性比較.….. 20 表2-3 Acrylates系統之多面體矽氧烷寡聚物(POSS) ………….… 21 表4-1多面體矽氧烷寡聚物POSS(MA0702)與MMA以不同比例共聚合,Td與殘留量一覽表………………………………………. 51 表4-2 圖4-20多面體矽氧烷寡聚物POSS與MMA以不同比例共聚合,Tg一覽表…………………………………………………. 57

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